Oxyalkylated polyepoxide-treated amine-modified thermoplastic phenol aldehyde resins, and method of making same



particularly petroleum emulsions. concerned with the application of such chemical products 'or compounds in various other arts and industries as well nited Sttes Patent OXYALKYLATED P OLYEP OXIDE TREATED AMINE-MODIFIED THERMOPLASTIC PHENOL ALDEHYDE RESINS, AN D METHOD OF MAK- ING SAME jMelvin De Groote, St. Louis, and Kwan-ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware .No'Drawing. Original application June 26, 1953, Serial The present invention is a continuation-in-part of our -copending application, Serial No. 338,576, filed February 24, 1953, now US. Patent 2,771,438 and a division of our copending application Serial No. 364,504, filed June 26, 1953, now US. Patent 2,771,428.

- Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, break- 2 linking radicals. Our preference is that either diphenyl compounds be employed or else compounds where the divalent link is obtained by the removal of a carbonyl oxygen atom as derived from a ketone or aldehyde.

- If it were not for the expense involved 'in preparing and purifying the monomer we would prefer it to any other form, i.e., in preference to the polymer or-mixture of polymer and monomer.

Stated another way, we would prefer to use materials 10 of the kind described, for example, in US. Patent No.

2,530,353, dated November 14, 1950. Said patent describes compounds having the general formula O 2 wherein R is an aliphatic hydrocarbon bridge, each in independently has one of the values and 1, and 'X is 20 an alkyl radical containing from 1 to 4 carbon atoms.

The compounds having two oxirane rings andemployed for combination with the reactive amine-modified. phenolaldehyde resin condensates as herein described are characterized by the following formula and cogeneriing or resolving emulsions of the water-in-oil type and ,cally associated compounds formed in their preparation:

H! 11 HI E2 H: H; -H)

Our invention is also '.Wil1h certain monoepoxides, also hereinafter described in detail.

Fora number of reasons it isusually most desirable to use the diepoxide type of polyepoxide. In preparing diepoxides or the low molal polymers one usually ob- .tains cogeneric materials which may include monoepoxides. However, the cogeneric mixture is invariably characterized by the fact that there is on the average,

based on the molecular weight, of course, morethan one epoxide group per molecule.

A more limited aspect of the present invention is represented by the products wherein the polyepoxide is represented by (1) compounds of the following formula:

and (2) cogeneric ally associated compounds formed in the preparation of (1) preceding, with the proviso that it consists principally of the monomer as distinguished from other cogeners.

Notwithstanding the .fact that subsequent data will be presented in considerable detail, yet the description becomes somewhat involved and certain facts should be kept in mind. The epoxides, and particularly the diepoxides may have no connecting bridge between the phenolic nuclei as in the case of a diphenyl derivative or may-have a variety of connecting bridges, i.e., divalent .in which R represents a divalent radical selectedfrom the class of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained by-the elimination of the aldehydic oxygen atom, the-'divalent radical H H oo H H 40 the divalent 0 ll ...C

radical, the divalent sulfoue radical, and the divalent monosulfide radical fiS, the divalent radical in which R, R",-and'R represent hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer including zero and 1 and-n represents a whole number not greater than 3. The abovementioned compounds and those cogenerically associated compounds formed in their preparation are thermoplastic and organic solvent soluble. Reference to being thermoplastic characterizes products as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents, .such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to .ditferentiate from a reactant which is not soluble and;might be not onlyinsoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with the amine resin condensate. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as, for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexy-l ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i.e.,

. the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2-epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4-epoxybutane (1,2-3,4 diepoxybutane) Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenol-aldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms 3 (condensate) in which the various characters have their previous signifi- -cance and the characterization condensate is simply an leveling agents in the laundry, textile and dyeing inabbreviation for the condensate which is described in greater detail subsequently.

Such intermediate product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of Water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base or the free base (combination with water) or a salt form which is the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking.

Not only does this property serve to differentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken 7 a mixture of xylene and methanol, for instance, 80 parts 76 of xylene and 20 parts of methanol, or parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone.

A mere examination of the nature of the products before and after treatment with the polyepoxide reveals that the polyepoxide by and large introduces increased hydrophobe character or, inversely, causes a decrease in hydrophile character. However, the solubility charac teristics of the final product, i.e., the product obtained by oxyalkylation of a monoepoxide, may vary all over the map. This is perfectly understandable because ethylene oxide, glycide, and to a lesser extent methyl glycide, introduce predominantly hydrophile character, while propylene oxide and more especially butylene oxide, introduce primarily hydrophobe character. A mixture of the various oxides will produce a balancing in solubility characteristics or in the hydrophile-hydrophobe character so as to be about the same as prior to oxyalkylation with the monoepoxide.

The oxyalkylated polyepoxide treated condensates obtained in the manner described are, in turn, oxyalkylation-susceptible and valuable derivatives can be obtained 25 by further reaction with other alkylene oxides, for instance, styrene (phenyl ethylene) oxide, cyclohexylethylene oxide, ethylene imine, propylene imine, acrylonitrile, etc.

Similarly, the oxyalkylated polyepoxide-derived compounds can be reacted with a product having both 2. nitro gen group and a 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See US. Patent No. 2,520,093, dated August 22, 1950, to Gross.

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-inoil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

(condensate) The new products are useful as wetting, detergent and dustries; as wetting agents and detergents in the acid washing of building stone and brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc. i

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i.e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufficiently hydrophile character to at least meet the test set forth in US. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble its presence manifest. the hereto appended claims as to the use of xylene in the M although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene glycol diethylether, ora low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such testis obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes It is understood the reference in emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into ten parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide and particularly the diepoxide reactant;

Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned-with the preparation of monomeric diepoxides, including Table I;

Part 3, Subdivision'B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation reaction to yield the amine-modified resin;

Part 5 is concerned with appropriate basic hydroxylated polyamines which may be employed in the preparation of the herein-described amine-modified resins;

Part 6 is concerned with reactions involving the resin,

.the amine, and formaldehyde to produce specific products,

orcompounds which are then subjected to reaction with polyepoxides;

Part 7 is concerned with the reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than a reaction between 2-rn0les f aipreviously prepared amine-modified phenol-aldehyde resin condensate as described, and one mole of a polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 8 is concerned with the use of a monoepoxide in oxyalkylating the products described in Part 7, preceding, i.e., those derived by means of'reaction between a poly- "epoxide and an amine-modified phenol-aldehyde resin as described;

Part 9 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products;

Part 10 is concerned with uses for the products herein described, either .as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 As will be pointed out subsequently, the preparation of "polyepoxides may include the formation of a small amountof material havingmore than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids. Indeed, they .tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any monoepoxides and as free as possible from polyepoxides in which there are moretthan two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

Ashas been pointed out previouslyone of the {reactants employed is a diepoxide reactant. It is generallyobtainejd from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of .the epoxides usually results in the formationof a co-generic mixture as explained subsequently. Preparation .of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been preparedand described in the literatureand-will be referredto subsequently. However, from a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to -be used for practical reasons areeither monomers with some small amounts of polymers present or mixtures which have a substantial amount Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commercially available and for most practical purposes it means instances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substit-uted monofunctional phenols with an aldehyde .illustrate the third class. All the various known classes may be used but our preference rests with theseclasses due .to

their availability and ease of preparation, and alsodue to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced in more than one way, as pointed out elsewhere, our preference is to produce them by means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds .tothe derivativeofbis-phenol A. It can be used as such, or the monomer can be separated by an added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactantand .willbe used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and'higher polymers are satisfactory. The formula for this compoundis Reference has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with the 4,4 isomers predominating and with lesser-quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attentionis. again directedto the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, what is said hereinafter, although directed to one class or a few classes, applies with equal product, or a mixture of products, which would be unusually toxic, even though in comparatively small concen- 8 PART 3 Subdivision A The preparations of the diepoxy derivatives of the diphenols, which are sometimes referred to as diglycidyl ethers, have been described in a number of patents. For convenience, reference will be made to two only, to wit, aforementioned U.S. Patent 2,506,486, and aforementioned U.S. Patent No. 2,530,353.

Purely by way of illustration, the following diepoxides, or diglycidyl ethers as they are sometimes termed, are included for purpose of illustration. These particular comtratlon. 15 pounds are described in the two patents ust mentioned.

TABLE I Ex- Patent ample Dlphenol Dlglyeldyl ether refernumber ence OH,(O H OH) Di(epoxypropoxyphenyl)methane 2,506,486 GH3OH(G@H;OH) Dl(epoxypropoxyphenyl)methylmethane... 2, 506,486 (CH3)2O(O5H4OH) Di(epoxypropoxyphenyl)dlrnethylmethane 2, 506, 486 CQH5C(CH3)(C6H4OH)I Di(epoxypropoxyphenylgethylmethylmethane 2,506,

Di(epoxypropoxyphenyl diethylmethane 2, 506,486 Di(epoxypropoxyphenyl)methylpropylmethane 2,506,486 Di(epoxypropoxyphenyDmethylphenylmethane 2,506,486 Di(epoxypropoxyphenyl)ethylphenylmethane 2, 506, 486 Di(epoxypropoxyphenyl)propylphenylmethane 2, 506,486 Di(epoxypropoxyphenyl)butylphenylmethane 2, 506, 486 Di(epoxyprepexyphenyl)tolylmet ane 2, 506,486 Di (epoxypropoxyphenyl) tolylmethylmethenm. 2, 506, 486 Dihydroxy dlpheu 4,4-bis(2,3-epoxypr0p0xy)dlphenyl 2,530,353 (0H3)C(O4H5.C6H3OH)Z 2,2-bls(4-(2,3-epoxypropoxy)Z-tertiarybutyl phenyDpropane.-. 2, 530, 358

PART 2 The polyepoxides and particularly the diepoxides can be derived by more than one method as, for example, the use of epichlorohydrin or glycerol dichlorohydrin. A number of problems are involved in attempting to produce these materials free from cogeneric materials of related composition. For a discussion of these difliculties,

reference is made to U.S. Patent No. 2,819,212, beginning at column 7, line 21.

Subdivision B TABLE II (in which the characters have their previous significance) Example -R O from HR1OH R- 'n n Remarks Number B1 Hydroxy benzene OH; 1 0,1,2 Phenol known as bis-phenol A. Low i polymeric mixture about or more -C- where n=0, remainder largely where I n=1, some where n=2. CHa 132....... ..do CH; 1 0, 1, 2 Phenol known as bis-phenol 13. See note (I regarding B1 above. I (311: CH; B3 Orthobutylphenol CH; 1 0, 1,2 Even though n is preferably 0, yet the l usual reaction product might well con- -C tain materials where n is 1, or to a I lesser degree 2. CH:

B4. Ortheemylphenol (311; 1 0, 1, 2 Do.

B5 Orthoectylphenol (IJH; 1 0,1,2 D0.

. ll ll Subdivision C The prior examples have been limited largely to those in which there is no divalent linking radical, as in the case of diphenyl compounds, or where the linking radical is derived from a ketone or aldehyde, particularly a ketone. Needless to say, the same procedure is employed in converting diphenyl into a diglycidyl ether regardless of the nature of the bond between the two phenolic nuclei. For purpose of illustration attention is directed to numerous other diphenols which can be readily converted to a suitable polyepoxide, and particularly diepoxide, reactant.

As previously pointed out the initial phenol may be substituted, and the substituent group in turn may be a cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon atoms. See U.S. Patent No. 2,515,907.

in which the -C H groups are secondary amyl groups. See U.S. Patent No. 2,504,064.

a ia See U. S. Patent No. 2,285,563.

See U.S. Patent No. 2,503,196.

wherein R is a member of the group consisting of alkyl, and alkoxyalkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U.S. Patent No. 2,526,545.

wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. See U.S. Patent No. 2,515,906.

HgC-Jf-CH: Hac |--CH3 CH3 C 9 See U.S. Patent No. 2,515,908. 1

As to sulfides, the following compound is of interest:

a n r n aldehyde or some other aldehyde, particularly compounds such as t,

A lkyl R Alkyl Alkyl Alkyl in which R is a methylene radical, or a substituted methylene radical which represents the residue of an aldehyde and is preferably the unsubstituted methylene radical derived from formaldehyde. See U.S. Patent No. 2,430,002.

See also U. S. Patent No. 2,581,919 which describes di(dialkyl cresol) sulfides which include the monosulfides, the disulfides, and the polysulfides. The following formula represents the various dicresol sulfides of this invention:

OH on. CH3 011 & R, R1 R1 R2 in which R and R are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R and R each preferably contain 3 to about 10 carbon-atoms,'-and x is 1 to 4. The term "sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 fmated in an idealized form by the formula on on on H n1 o H 1140 R R n R In the above formula n represents a small Whole number varying from 1 to '6, 7, or 8, or more,up to probably or 12 units, particularly whenthe resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i.e., n varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to carbon atoms, such as a butyl, amyl, hexyl, decyl, or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, even when obtained from a difunctional phenol, for instance paraphenylphenol, one may obtain a resin" which is not soluble in a nonoxygenated solvent, such as-benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and nonoxygenated) will serve. See Example 9a of U.S. Patent No. 2,499,365, dated March 7, -1950, to De Groote and Keiser.

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such 'asbenzene or xylene. This presents no probleminsofar that-all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U.S. Patent No. 2,499,365, or in U.S. Patent No. 2,499,368, dated March '7, 1950, to De Groote and Keiser. In said patent there are described oxy-alkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water-insdluble, low-stage phenol-aldehyde resins having an average molecular weight corresponding to at least 3'and -not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-forming 'reactivity, are derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol, and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula in which R is an aliphatic hydrocarbon radical having at 'least 4 carbon atoms and not more than 24 carbon atoms,

ously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic hydroxylated polyamine as specified, following the same 14 idealized overesimplification previously referred to, "the resultant product might 'beillustrate'd thus:

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield .forobvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one'mole of the amine may combine with the-resin molecule, or'even to a very slight extent, if at all, 2-resin units may combine without any amine in thereaction-product, as indicated in the following formulas:

'As has been pointed out previously,as faras the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit maybe exemplified thus:

on Rm on R R R .in which R' is the divalent radical obtained from the particular aldehyde employed to form the resin. For

reasons which are obvious the condensation productobtained appears to be described best in terms of the method of manufacture.

Aspreviously stated the preparation of resins, the

catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Simiv.larly, if a strong base is used as a catalyst it is preferable that the base be neutralized although we have-found that sometimes the reaction described proceeded more rapidly .inthe presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used.

However, the most desirable procedure in practically every case isto have the resin neutral.

'In preparing resins one does not get a single polymer, i.e., one having just'3 units, or just 4 units, or just 5 units, orjjustj6units, .etc. lItiistusually.a;mixture;3for

-2,sse,eso

- instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no TABLE III M01. Wt. Ex Position R of Resin ample R of R derived 1: Molecule number from (based on n+2) Tertiary butyl Para... Formal- 3. 5 882. 5

Secondary buty1 3. 5 882. 5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary amyl.

3. 5 805. 5 3. 5 1, 036. 5 ct l 3. 5 1, 190. 5 NonyL. 3. 5 1, 267. 5 DeeyL. 3. 5 1, 344. 5 Dodecyl 3. 5 1, 498. 5 Tertiary butyl 3. 5 945. 5

Tertiary amyl 3. 5 1, 022. 5 Nonyl 8. 5 1, 330. 5 Tertiary butyl 3. 5 1, 071. 5

Tertiary amyl 3. 5 1, 148. 5 Nony do 3. 5 1, 456. 5 Tertiary butyl Propional- 3. 5 1, 008. 5

dehyde. Tertiary arnyl o 3. 5 1, 085. 5 Nouyl 3. 5 1, 393. 5 Tert ary butyl 4. 2 996. 6

- Tertiary amyl 4. 2 1, 083. 4 N onyl 4. 2 1, 430. 6 Tertiary butyl 4. 8 1, 094. 4 Tertiary amyl 4. 8 l, 189. 6 4. 8 l, 570. 4 l. 5 604. O 1. 5 653.0 1. 5 688.

PART 5 As has been pointed out, the amine herein employed as a reactant is a hydroxylated basic polyamine and preferably a strongly basic polyarnine having at least one secondary amino radical, free from primary amino groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl, alicyclic, arylalkyl, or heterocyclic in character, subject of course to the inclusion of a hydroxyl group attached to a carbon atom which in turn is part of a monovalent or divalent radical.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. They can be obtained by hydroxylation of low cost polyam-ines. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as many as 5, 6 or 7 nitrogen atoms. Such amines are susceptible to terminal alkylation or the equivalent, i.e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amine group. In the same way, the polyamines can be subjected to hydroxyalkylation by re action with ethylene oxide, propylene oxide, glycide', etc.

. In some instances, depending on the structure, both types of reaction may be employed, i.e., one type to introduce a hydroxy ethyl group, for example, and another type to introduce a methyl or ethyl radical.

By way of example the following formulas are included. It will be noted they include such polyamines which, instead of being obtained from ethylene dichloride, propylene dichloride, or the like, are obtained from dichloroethyl ethers in which the divalent radical has a. carbon atom chain interrupted by an oxygen atom:

CH3 CH3 No nigolrnN C Hr CgHG H0 CQHA H NpropyleneNpropyleneN HOC Hr CQHAOH CH CH3 HOCgHA C EhOH HOCQE 0 11 011 Another procedure for producing suitable polyamines is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an alkylene oxide, such as ethylene oxide, propylene oxide or glycide.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylene oxide followed by reaction with an imine and then the use of an alkylene oxide again. Similarly, one can start with a primary amine and introduce two moles of an alkylene oxide so as to have a compound comparable to ethyl diethanolamine and react with two moles of an imine and then with two moles of ethylene oxide.

Reactions involving the same reactants previously described, i.e., a suitable secondary monoarnine plus an alkylene imine plus an alkylene oxide, or a suitable monoamine plus an alkylene oxide plus an alkylene imine and plus the second introduction of an alkylene oxide, can be applied to a variety of primary amines. In the case of primary amines one can either employ two moles of an alkylene oxide so as to convert both amino hydrogen atoms into an alkanol group, or the equivalent; or else the primary amine can be converted into a secondary amine by the alkylation reaction. In any event, one can obtain a series of primary amines and corresponding secondary amines which are characterized by the fact that such amines include groups having repetitious ether linkages and thus introduce a definite hydrophile efiect m mes by virtue of the ether linkage. Suitable polyether amines Susceptible to conversion in the manner described include those of the formula in which x is a small whole number having a value of l or more, and may be as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numeral 1 to 2; and m represents a number to 1, with the proviso that the sum of in plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical.

The preparation of such amines has been described in the literature and particularly in two United States patents, to wit, U.S. Nos. 2,325,514, dated July 27, 1943, to Hester, and 2,355,337, dated August 8, 1944, to Spence. The latter patent describestypical haloalkyl ethers such CH30 C HqCl CH;OH

OH; CH 'CH2O O H O C H Br Such haloalkyl ethers can react with ammonia, or with a primary amine such as methylamine, ethylamine, cyclohexylamine, etc., to produce a secondary amine of the kind above described, in which one of the groups attached to nitrogen is typified by R. Such haloalkyl ethers also can be reacted with ammonia to give secondary amines as described in the first of the two patents mentioned immediately preceding. Monoamines so obtained and suitable for conversion into appropriate polyamines are exemplified by Other similar secondary monoamines equally suitable for such conversion reactions in order to yield appropri ate secondary amines, are those of the composition R-O(OHZ)3 RO(CH2)3 as described in US. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in US. Patent No. 2,482,546, dated September 20, 1949, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples include the following: beta phenoxyethylamine, gamma-phenoxypropylamine, beta-phenoxy-alpha-methylethylamine, and beta-phenoxypropylamine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517, and may be illustrated by C H -0-CH CH -OCH -CH NHCH In light of the various examples of polyamines which 18 currence of R must include a secondary amino radical of the kind specified. Actually, if the polyamine radical contains two or more secondary amino groups the amine may be reactive at two different positions and thus the same amine may yield compoundsin which R and R are dissimilar.

H CgHrOH on, on,

HOC H, O H OH In the first of the two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atom, which inturn combines with the methylene bridge, would be difierent than if the reaction took place at the intermediate secondary amino radical as diiferentiated from the terminal group. Again, referringto the second formula above, although a terminal amino radical is not involved it is obvious again that one could obtain two difierent structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending on whether the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part atv another point. Indeed, there are'well known suitable polyamine reactions Where a large variety of compounds might be obtained due to such multiplicity of reactive radicals. This canbe illustrated by the following formula:

H EHdOH Certain hydroxylated'polyamines which may be employed and which illustrate the appropriate type of reactant used for the instant condensation reaction may be illustrated by the following additional examples:

HOCH CH NHCH assasso As is well known one can prepare ether amino alcohols of the type ROCH CH OH) CH NHCH CH NHCH CH (OH) CH -OR in which R represents an alkyl group varying from methyl to normal decyl, and in fact, the group may contain as many as 15, 20 or even 30 carbon atoms. See J. Org. Chem, 17, 2 (1952).

Over and above the specific examples which have appeared previously, attention is directed to the fact that a number of suitable amines are included in subsequent Table IV.

PART 6 The products obtained by the herein described processes represented cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difi-icult to actually depict the final product of tllfie cogeneric mixture except in terms of the process 1tse Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-alde hyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to 150 C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U.S. Patent No. 2,499,368. In mose instances the resin selected is not apt to be a fu-- sible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it convenient to use a solvent and particularly one which can be removed readily at a compara-- tively moderate temperature, for instance, at C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a Way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively nonvolatile solvent such as dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in any oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually, water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used but it is more difiicult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction. However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent need not be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is whethehr or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some of the initial solvent is apt to remain Without complete removal. Even if one starts with a resin which is almost invariably a dark red in color or at least a red-amber, or some color which includes both an amber component and a reddish component. By and large, the melting point is apt to be lower and the products may be more sticky and more tacky than the original resin itself. Depending on the resin selected and on the amine selected the condensation product or reaction mass on a solventfree basis may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water-insoluble or water-dispersible, or water-soluble, or close to being Water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for instance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid, etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 150 C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc.,

use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass Without removal?; (1)) is the reaction mass to' be sub jected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation?; and the third factor is this, (c) is an effort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove any unreacted water-soluble polyamine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found Xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and

for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of-heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually solublethenagitationshould be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employedis invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form, is completely s'oluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U.S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. Ifit is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible thatthe initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture-, ifnot completely soluble is cooled" t at least the reaction temperature or "somewhat below, for example C. or slightly lower, provided this initial low temperature stage is employed. The

reasonspointed out we prefer to use a solution and I whether to -use a commercial 37% concentration is simply a matter of choice.

In large scale manufacturing there may be some advantage in using a 30% solution of formaldehyde but-, apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure'employing a glass resin pot, when the reaction has proceeded as far as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or 5 hours,

or at the most, up to 10-24 hours, we then complete the reaction by'raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C., and below 15 0 C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continueduntil the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U.S. Patent No. 2,499,368.

Needlessto say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances we have added atrace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine and, again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some "instances have checked Whether or not the end-product showed surface-activity, particularly in a dilute acetic acidsolution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

In light of What has been said previously little more need be said as to the actual procedure employed for the preparation of'the herein described condensation proddots. The following example will serve by way of illustration:

Example 1]) The-phenol-aldehyde resin is the one that has been identified previously as Example 1a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei as the value for n which excludes the 2 external nuclei, i.e., the'resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overallnuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as la preceding, were powdered and mixed with a considerably lesser weight of xylene, to wit, 500 grams. The mixture was 23 refluxed until solution was complete. It was then adjusted to approximately 33 to 38 C., and 296 grams of symmetrical di(hydroxyethyl)ethylenediamine were add- 24 As to the formulas of the above amines referred to as Amine A through Amine I, inclusive, see immediately following:

ed. The mixture was stirred vigorously and formalde- HOOH; OzHiOH hyde used was a 30% solutlon and the amount employed 5 was 200 grams. It was added in a little over 3 hours. Amine A NC=H4N The mixture was stirred vigorously and kept within a H H temperature range of 33 to 48 C. for about 17 hours. B 11, 0511 011 At the end of this time it was refluxed using a pl 1ase Amine NCHN separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of formal- H H dehyde was noted. Any unreaeted formaldehyde seemed 11001734 CaHIOH to disappear within about 3 hours or thereabouts. As mine N H N soon as the odor of formaldehyde was no longer particularly noticeable or detectible the phase-separating trap mm was 1setthso as to eliminate pagt 3f the xylene was 1l'esrggvecd 1e CHFCH, Q untl e temperature reac e approxlmatey H N or perhaps a little higher. The reaction mass was kept HO O NH CHCHF H O HO OH at this temperature for a little over 4 hours and the CHPCHB rreaction stopped. During this time any additional water, 0 CH5 H N(C=H1OH)5 which was probably water of reaction which had formed, Amine was eliminated by means of the trap. The residual CH CH xylene was permitted to stay in the cogeneric mixture.

A small amount of the sample was heated on a Water CH3 bath to remove the excess xylene. The residual mate- 5 Amine F rial was dark red in color and had the consistency of a HO9HHOCHZCHNHTCHrOTCZHTOTCHTNHCHCHOH sticky fluid or tacky resin. The overall time for reac- Amme HOCHGHYNHCHQCHOHCH= NHOHGHNH tion was somewhat under hours. In other examples HOCH1CHKNHCH= it varied from 24 to more than 36 hours. The time can 30 Amine HoomcnmH-on be reduced by cutting the low temperature period to ap- HOCHIOHQNH H: proximately 3 to 6 hours. Note that in Table IV 1501- CHNHOH lowing there are a large number of added examples illusa trating the same procedure. In each case the initial mix- Amine I- OHiNHGHiOHi0H ture was stirred and held at a fairly low temperature OHSNHOH: (30 to C.) for a period of several hours. Then 35 refluxing was employed until the odor of formaldehyde PART 7 pp Aftfil' the Odor of formaldehyde P- The products obtained as herein described by reactions Pfiared the Phase-Separating p f p y to fp involving amine condensates and diglycidyl ethers or the rate out all Th6 Watfif, bOth the SOllllllOIl and condensation. equivalent are valuable for use as such is pointed After an the wamf had been separated enough Xylene was out in detail elsewhere. However, in many instances the takm out to 113V? the final Product IefluX for Several derivatives obtained by oxyalkylation are even more valhours Somewhere In thB range of 145 t0 uable and from such standpoint the herein described thereabouts. Usually the mlxture yielded a clear soluroduct may be considered as valuable intermediates. tlon by the time the bulk of the water, or all of the wa- Subsequent oxyalkylation involves the use of ethylene ter, had been removed. oxide, propylene oxide, butylene oxide, glycide, etc. Note that as pointed out previously, this procedure is Such oxyalkylating agents are monoepoxides as differenillustrated by 24 examples in Table IV. tiated from polyepoxldes.

TABLE IV Strength of Reac- Reao- Max. Ex. Resin Amt, Amine used and amount formalde- Solvent used tion tion distill. N0. used grs. hyde soln. and amt. temp., time, temp.,

and amt. 0. hrs. 0.

882 Amine A 296 g 30% 200 15.... Xylene 500 g- 21-24 24 150 480 Amine A 143 g 37% 31 g Xylene 430 g-. 20-23 27 156 53s Amine A 148 g 37% 81 g. Xylene 610 22-27 25 142 411 Amine B 175 g 30% Xylene 300 g- 20-25 28 480 Amine B 170 g 37% 31 g Xylene 425 g 23-27 34 533 Amine B 170 g- H 30% 100 g- Xylene 500 g- 25-27 30 152 322 Amine o 324 g 37% 102 g Xylene 625 23-20 38 141 430 Amine o 162 g 1 30% 100 Xylene 315 g 20-21 25 143 033 Amine 0 102 g 30% 100 g- Xylene 535 g 23-24 25 140 473 Amine D 253 g 30% 100 g- Xylene 425 g 22-25 25 143 511 Amine D 256 g 30% 100 Xylene 450 g 20-21 25 158 665 Amine D 256 g 30% 100 g Xylene 525 g 21-25 28 152 441 Amine E 208 g 37% 81 g. Xylene 400 g.- 22-24 26 143 430 Amine E 203 g- .1 37% 31 g Xylene 400 25-27 36 144 505 Amino E 208 g 37% 81 g Xylene 500 g. 26-27 34 141 441 Amine F 236 g h 37% 81 g Xylene 400 g 21-23 25 153 480 Amine F 236 g- 37% 81 g Xylene 400 g 20-22 28 150 511 an lne F 2311 g 37% 81 g.. Xylene 500 g- 23-25 27 155 498 Amine G 172 g 37% 81 g Xylene 400 g. 20-21 34 150 542 Amine G 172 g. 37% 81 g Xylene 450 g 20-24 36 152 547 Amine H 221 g- 37% 81 g. Xylene 500 g. 20-22 30 148 441 Amino H 221 g 37% 81 g Xylene 400 g 20-29 24 143 595 Amine I 172 g 37% 81 g- Xylene 450 g 20-22 32 151 391 Amine I 35 g--- 30% 50 g Xylene 300 g 20-26 36 147 25 It becomes apparent that if the product obtained is to be treated subsequently with a monoepoxide which may require a pressure vessel as in the case of ethylene oxide, it is convenient to use thesame reaction vessel in both 2d Resin 3a was obtained from tertiary amylphenol and formaldehyde. The amount of resin employed was 480 grams. The amount of amine employedtAmine A) was 148 grams. The amount of 37% formaldehydeeminstances. In other words, the 2 moles of the amine- 5 pleyed s 81 grainsamount of solvent p y modified phenol-aldehyde resin condensate would be rewas 0 AmineA, as Previously indicated a the acted with a polyepoxide and then subsequently with a end of Table IV, preceding, was symmetrical di(hymonoepoxide. In any event, if desired thepolyepoxide d y yn y diamillfix All this s ee ereaction can be conducted in an ordinary reaction vessel, S be previously. such as the usual glass laboratory equipment. This is The solution of the condensate in xylene was adjusted particularly true of the kind used for resin manufacture to a coilceiitfatiolln this Particular instance, and as described in a number of patents, as for example, in Practically all the Others Which appear in i116 Subse- U.S. Patent No. 2,499,365. quent table, the examples are characterized by the fact cognizance should be taken of one particular feature that no alkaline catalyst was added. The reason is, of in connection with the reaction involving the polyepoxide Course, that the Condensate as Such is Strongly basicand that is this; the amine-modified phenol-aldehyde resin It desil'ed, a Small amount f alkaline a ly t 0 11 be condensate is invariably basic andthus one need notadd added, such as finely powdered caustic soda, sodium the usual catalysts which are used to promote such ret y etc f h alkaline catalyst is added it y actions. Generally speaking, the reaction will proceed speedup the reaction but it also may cause an undesirable at a satisfactory rate under suitable conditions without reaction, Such as the Polymerization of the diePOXideany catalyst at all. In any event, 128 grams of the condensate were dis- Employing polyepoxides in combination with a non- Solved n aPPTOXiIIIatdY all equal Weight of Xylene and basic reactant the usual catalyst include alkaline mastirred and heated to 100 C. 17 grams of the diepoxide terials such as caustic soda, caustic potash, sodium previously identified as 3A, and dissolved in an equal methylate, etc. Other catalysts may be acidic in nature Weight of xylene, were added dropwise. The initial addiand are of the kind characterized by iron and tin chlotion of the xylene solution carried thetemperature above ride. Furthermore, insoluble catalysts such as clays or 109 C. The remainder oft e dielmXide Was addedlifl specially prepared mineral catalysts have been used. If a t an rs m uri g his period Oftime the for any reason the reaction did not proceed rapidly temperaturerose somewhere above 120 C. The prodeuough with the diglycidyl ether or other analogous renot was allowed to reflux at about 130 C., using a phaseactant, then a small amount of finely divided caustic soda Separating trap. A Small amount of Xylene Was removed or sodium methylate could be employed as a catalyst. by ans of e p ase-separ ing trap as the tempera- The amount generally employed would be 1% or 2%, mm gradually rose to 170 C. or slightly'less. The mix- It goes Without saying that the reaction can take place ture was then refluxed at about this same temperature in an inert solvent, i.e., one that is not oxyalkylation- 01 ab ut 4 Or 5 h urs until the reacti n had stopped susceptible. Generally speaking, this is more convenand' the xylene which had been separated out during the iently an aromatic solvent such as xylene ora higher reflux period, was returned to the mixture. The overall boiling coal tar solvent, or else a similar high boiling reaction time was about 7 hours. A small amount of aromatic solvent obtained from petroleum. One can material was withdrawn and the xylene evaporated on a employ an oxygenated solvent such as the diethylether 40 hot plate in order to examine the physical properties. of ethylene glycol, or the diethylether or propylene gly- The material was a dark red viscouse semi-solid. It was col, or similar others, either alone or in combination with insoluble in Water, it Was insoluble in a 5% gluconic acid a hydrocarbon solvent. The selection of the solvent desolution, and it was soluble in xylene, and particularly pends in part on the subsequent use of the derivatives or in a mixture of 80 parts xylene and 20 parts methanol. reaction products. If the reaction products are to be However, if the material was dissolved in an oxygenated rendered solvent-free and it isnecessary thatthe solvent solvent and then shaken with 5% gluconic acid it showed be readily removed as, for example, by the use of vacua definite tendency to disperse, suspend, or form a sol um distillation, thus xylene or an aromatic petroleum will and particularly in a xylene-methanol mixed solvent as Serve If the Product is going to be Subjected to Y- previously described, with or without the further addialkylation subsequently, then the solvent should be one {ion f litfl aceuma which is not oxyalkylation-susceptible. It is easy enough The procedure employed of course is Simple in light to select a suitable solvent if required in any instance of What has been Said previously and in effect is a y everythmg 618a equal the solvent chosen cedure similar to that employed in the use of glycide or S Ould be the most economical methylglycide, as oxyalkylating agents. See, for example Example 10 Part 1 of US. Patent No. 2,602,062 dated July 1, 1952, The product was obtained by reaction between the dito De Grooteid previously d i d as di id 3 and Various examples obtained 1n substantlally the same densate 2b. Condensate 2b was obtained from resin 3a. manner are enumerated in the following tables:

TABLE V Con- Diep- Time Max. Ex. den- Amt, oxide Amt., Xylene, Molar 0t reactemp, Color and physical state No. sate grs. used grs. grs. ratio tion, C.

used hrs.

10...- 128 3A 17 2:1 7 170 Dark semi-s0lid 20..-. 131 3A 17 2:1 8 168 Do. 123 3A 17 140 2:1 7 175 D0. 40..-. 130 3A 17 147 2:1 7 172 D0. 50.... 148 3A 17 2:1 8 168 3 Do. 00..-- 187 A 17 204 2:1 8 175 Dark solid mass 70-..- 132 3A 17 150 2:1 s 108 130. so 152 3A 17 2:1 8 170 D0. 90-.-- 136 3A 17 153 2:1 8 165 7 Do. 10 .145 3A 17 102 2:1 8 170 D0.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 10.

TABLE VI Con- Diep- Time Max. Ex. den- Amt., oxide Amt., Xylene, Molar of reactemp., Color and physical state No. sate grs. used grs. grs. ratio tion, 0.

used hrs.

128 B1 27.5 156 2:1 7 165 Dark semi-solid 134 B1 27.5 162 2:1 7 170 D0. 123 B1 27, 2: 1 7 170 D0. 130 B1 27.5 158 2:1 7 175 Do. 148 B1 27. 5 176 2: 1 8 172 Do. 187 B1 27. 5 215 2: 1 8 168 Dark solid mass 132 B1 27. 5 160 2:1 7 D0. 152 B1 27. 5 180 2: 1 8 D0. 136 B1 27. 5 164 2:1 8 165 Do. 145 B1 27. 5 173 2: 1 8 D0.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 10.

TABLE VII Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex. No. densate reaction product, solvent, hydroxyls used product grs. grs. per molecule TABLE VIII Probable Probable Resin conmol. wt. of Amt. of Amt. of number of Ex. No. densate reaction product, solvent, hydroxyls used product grs. grs. per molecule At times we have found a tendency for an insoluble mass to form or at least to obtain incipient cross-linking or gelling even when the molal ratio is in order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such as xylene or the like. In some instances an oxygenated solvent, such as the diethyl ether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of catalyst used, or reduce the temperature of reaction by adding a small amount of initially lower boiling solvent such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepoxide, for instance, 90% or 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular weight by several percent.

Previously the condensates has been depicted in a siinplified form which, for convenience, may be shown thus:

(Amine) CH (Resin) CH (Amine) Following such simplification the reaction product with a polyepoxide and particularly a diepoxide, would be indicated thus:

[(Amine) GHKResin) CH2 (Amine)] [D.G.E.]

[(Amine) CH:(Resin) CH:i(Amine)1 in which D.G.E. represents a diglycidyl ether as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated amine or polyamine, having a multiplicity of secondary amino groups it is obvious that other side reactions could take place as indicated by the following formulas:

[(Amlne) C H2 (Amine) [D G.E .1

[(Amine) CH2 (Amine)] [(Resin) CHa(Resi n)] [D GE .1

[(Resin) OHn(Resln)] [(Amine) CH:(Amine)] [D G .E .1

All the above indicates the complexity of the reaction product obtained after treating the amine-modified resin condensate with a polyepoxide and particularly diepoxide as herein described.

PART 8 The preparation of the compounds or products described in Part 7, preceding, involves an oxyalkylating agent, to wit, a polyepoxide and usually a diepoxide. The procedure described in the present part is a further oxyalkylation step but involves the use of a monoepoxide or the equivalent. The principal difierence is only that while polyepoxides are invariably nonvolatile and can be reacted under a condenser, at least numerous monoepoxides and particularly ethylene oxide, propylene oxide, butylene oxide, etc., involve somewhat different operating conditions. Glycide and methylglycide react under practically the same conditions as the polyepoxides. Actually, for purpose of convenience, it is most desirable to conduct the previous reaction, i.e., the one involving the polyepoxide, in equipment such that subsequent reaction with monoepoxides may follow without interruption. in the oxyalkylations carried out to produce compositions used in accordance with the present application, conventional equipment, i.e., a stainless steel autoclave suitably equipped, and conventional oxyalkylation conditions were used.

The amount of monoepoxides employed may be as high as 50 parts of monoepoxide for one part of the polyepoxide treated amine-modified phenol-aldehyde condensation product.

Example 1E The polyepoxide-derived oxyalkylation-susceptible compound employed is the one previously designated and described as Example 1D. Polyepoxides-derived condensate ID was obtained, in turn, from condensate 25 and diepoxide Bl. Reference to Table IV shows the composition of condensate 2b. Table IV shows it was obtained from Resin 5a, Amine A and formaldehyde. Amine A is symmetrical di(hydroxyethyl)-ethylene diamine. Table III shows that Resin 5a was obtained from tertiary amylphenol and formaldehyde.

to insure complete reaction.

' sions.

" For purpose of convenience, reference hereinand in the tables to the -oxyalkylation-susceptible compound will be abbreviated in the tablelteading as OSC; reference is tothe solvent-free material since, for convenience, the

amount of solvent is noted in a second column. Actually,

. part of the solvent may have been present and in practically every case was present in either the resinification process or thecondensation process, or in treatment with a polyepoxide. present at the time of treatment with a monoepoxide is In any event,;the--amount of solvent indicated as a separate item. To be consistent, of course, the oxyalkylation-susceptible compound abbreviated as OSC is indicated on a solvent-free basis.

--15.55 pounds of the polyepoxide-derived'condensate lar weight was approximately 4650.

Adjustment was made in the autoclave to operate at a temperature of 125 to 130 C., and at a pressure of to pounds per square inch.

The time regulator was set so as to inject the ethylene oxide in approximately one-half hour and then continued stirring for one-half hour longer simply as a precaution The reaction Went'readily and, as a matter of fact, the ethylene oxide could have been injected in probably 15 minutes instead of a halfhour and the subsequent time allowed to insure com- -lpletion of reaction. a matter of fact, the ethylene oxide could have been injected in probably 15 minutes instead of a half-hour and .the subsequent time allowed to insure completion of re- The-reaction went readily and, as

action may have been entirely unnecessary. The speed of reaction, particularly at the low pressure, undoubtedly was due in a large measure to the excellent agitation and also to the comparatively high concentration of catalyst.

The-amount of ethylene oxide introduced, as previously noted, was 7.75 pounds.

' A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility "or emulsifying power was concerned, and also for the purpose of making some tests on various oil field emul- The amount withdrawn was so small that no cognizance of this fact is included in the data or subsequent data, or in data reported in tabular form in subsequent Tables IX, X and XI.

The size of the autoclave employed was 35 gallons.

.In innumerable oxyalkylations we have withdrawn a substantial portion vat the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to 'oxyalkylation with a different oxide.

Example 2E This example simply illustrates further oxyalkylation of Example 1E, preceding. The oxyalkylation-susceptible compound, to wit, Example 1D, isthe same one as was used in Example 1E, preceding, because it is merely a continuation. In the subsequent tables, such as Table IX, the oxyalkylation-susceptible compound in the horizontal line concerned with Example 2E refers to oxyalkylationsusceptible compound, Example 1D. Actually, one could refer just as properly to Example 1E at this stage. It is immaterial which designation is used so long as it is understood and such practice is used consistently throughout the tables. In any event, the amount of ethylene oxide is the same as before, to Wit, 7.75 pounds. This means the amount of oxide at the end was 15.5 pounds. It is meant that the ratio of oxide to oxyalkylation-susceptible compound (molar basis) at the end was 70 .to 1. The

I theoretical molecular weight was almost 6,200. There 'was no added solvent. :In other words, it remained-the same, that is, 15.60- pounds, and there was no added hour, the same as before.

Example 3E The oxyethylation proceeded in the same manner as described in Examples/1E and 2E. There was no added solvent and no added catalyst. The oxide added was- 7.75 pounds. The totaloxide at the'end of the oxyalkylation procedure was 23.25 pounds. The vmolal ratio of oxide to condensate was 105 to l. The theoretical molecular weight was approximately 7,750. As previously noted, conditions in regard to temperature and pressure were the same as in Examples 1E and 2E. The time period was 45 minutes.

Example 4E The 'oxyethylation was continued and the amount of oxide added was the same as before, to wit, 7.75 pounds. The amount of oxide added at the end' of the reaction was 31.0.v There was 'noladded solvent and no added catalyst. Conditions as far as temperature and pressure are concerned'were the same as in previous examples. The time period was slightly longer, to wit, one hour. The reaction at this point showed modest, if any, tendency to slow up. The molal ratio of oxide to oxyalkylation-susceptible compound was about 140 to 1 and the theoretical molecular weight was 9,300.

' Example 5E Theoxyalkylation :was continued with the introduction of 15.5 pounds of oxide. The amount of oxide'at the end of this period was 46.5 pounds. No added solvent was introduced, and likewise no added catalyst was introdnced. 'The theoretical molecular weight at the end of the reaction was approximately 12,500. The molal ratio of oxide to oxyalkylation-susceptible compound was 210 to 1. The time period was two hours.

Example 6E The same procedure was followed as in the previous examples without addition of either more catalyst or more solvent. The amount of oxide added wasthe same as before, to wit, 15.5 pounds. The time required to complete the reaction was two and one-half hours. The total amount of oxide at the end ofthe period was 62 pounds. At the end of the reaction the ratio of oxide to oxyalkylation-susceptible compound was approximately 280 to 1, and the theoretical molecular weight was about 15,500.

The same procedure as described in the previous examples was employed in connection with a number of the other condensations described previously. All these data have been presented in tabular form in Tables IX through XIV, inclusive.

In substantially everycase a 35-gallon autoclave was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a 25-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered caustic soda.

Referring now to Tables IX, X and XI, it will be noted that compounds 1E through 18E were obtained by the use of ethylene oxide, whereas Examples 19E through 36E were obtained by the use of propylene oxide; and Examples 37E through 54E were obtained by'theuse of butylene oxide.

Referring now to Table X specifically, it will be noted that the series ofexamples beginning with 'lF were obtained, in turn, by use of both ethylene and propylene assaaso 31 oxides, using ethylene first; in fact, using Example 3E as the oxyalkylation-susceptible compound in the first six examples. This applies to series 1F through 18F.

Similarly, series 19F through 36F involve the use of both propylene oxide and ethylene oxide in which the propylene oxide was used first, to wit, 19E was prepared from 24E, a compound which was initially derived by use of propylene oxide.

Similarly, Examples 37F through 54F involve the use of ethylene oxide and butylene oxide, the ethylene oxide being used first. Also, these two oxides were used in the series 55F through 72F, but in this latter instance the butylene oxide was used first and then the ethylene oxide.

Series 73F through 90F involve the use of propylene oxide and butylene oxide, butylene oxide being used first and propylene oxide being used next.

In series 16 through 18G the three oxides were used.

It will be noted in Example 16 the initial compound was 78F; Example 78F, in turn, was obtained from a compound in which butylene oxide was used initially and then propylene oxide. Thus, the oxide added in the series 1G through 6G was by use of ethylene oxide as indicated in Table XI.

Referring to Table XI, in regard to Example 19G it will be noted again that the three oxides were used and 19G was obtained from 58F. Example 58F, in turn, was obtained by using butylene oxide first and then ethylene oxide. In Example 196 and subsequent examples, such as 20G, 216, etc., propylene oxide was added.

Tables XII, XIII and XIV give the data in regard to the oxyalkylation procedure as far as temperature and pressure are concerned and also give some data as to solubility of the oxyalkylated derivative in water, xylene and kerosene.

Referring to Table IX in greater detail, the data are as follows: The first column gives the example numbers, such as 1E, 2E, 3E and 413, etc.

The fifth column can be ignored for the reason that it is concerned with propylene oxide only, and the sixth column can be ignored for the reason that it is concerned with butylene oxide only.

The seventh column shows the catalyst which is invariably powdered caustic soda. The quantity used is indicated.

The eighth column shows the amount of solvent which is xylene unless otherwise stated.

The ninth column shows the amount of oxyalkylationsusceptible compound which in this series is the polyepoxide-derived condensate.

The tenth column shows the amount of ethylene oxide in at the end of the particular step.

Column eleven shows the same data for propylene oxide, and column twelve for butylene oxide. For obvitzgsE reasons these can be ignored in the series 1E through Column thirteen shows the amount of the catalyst at the end of the oxyalkylation step, and column fourteen shows the amount of solvent at the end of the oxyalkylatron step.

The fifteenth, sixteenth and seventeenth columns are concerned with molal ratio of the individual oxides to the oxyalkylatiOrr-susceptible compound. Data appears only in column fifteen for the reason, previously noted, that no butylene or propylene oxide were used in the present instance.

The theoretical molecular weight appears at the end of the table which is on the assumption, as previously noted, as to the probable molecular weight of the initial compound, and on the assumption that all oxide added during the period combined. This is susceptible to limitations that have been pointed out elsewhere, particularly in the patent literature.

Referring now to the second series of compounds in Table IX, to wit, Examples 19E through 36E, the situation is the same except that it is obvious the oxyalkylating agent used was propylene oxide and not ethylene oxide. Thus, the fourth column becomes a blank and the tenth column becomes a blank and the fifteenth column becomes a blank, but column five, which previously was a blank in Table IX now carries data as to the amount of propylene oxide present at the beginning of the reaction. Column eleven carries data as to the amount of propylene oxide present at the end of the reaction, and column sixteen carries data as to the ratio of propylene oxide to the oxyalkylation-susceptible compound. In all other instances the various headings have the same significance as previously.

Similarly, referring to Examples 37E through 54E in Table IX, columns four and five are blanks, columns ten and eleven are blanks, and columns fifteen and sixteen are blanks, but data appear in column six as to butylene oxide present before the particular oxyalkylation step. Column twelve gives the amount of butylene oxide present at the end of the step, and column seventeen gives the ratio of butylene oxide to oxyalkylation-susceptible compound.

Table X is in essence the data presented in exactly the same way except the two oxides appear, to Wit, ethylene oxide and propylene oxide. This means that there are only three columns in which data does not appear, all three being concerned with the use of butylene oxide. Furthermore, it shows which oxide was used first by the very fact that reference to Example IP, in turn, refers to 3E, and also shows that ethylene oxide was present at the very first stage. Furthermore, for ease of comparison and also to be consistent, the data under Molal Ratio in regard to ethylene oxide and propylene oxide goes back to the original diepoxide-derived condensate 1D. This is obvious, of course, because the figures 105.6 and 17.25 coincide with the figures for 1E derived from ID, as shown in Table IX.

In Table X the same situation is involved except, of course, propylene oxide is used first and this, again, is perfectly apparent. Three columns only are blank, to wit, the three referring to butylene oxide. The same situation applies in examples such as 37F and subsequent examples where the two oxides used are ethylene oxide and butylene oxide, and the table makes it plain that ethylene oxide was used first. Inversely, Example 55F and subsequent examples show the use of the same two oxides but with butylene oxide being used first as shown on the table.

Example 73F and subsequent examples relate to the use of propylene oxide and butylene oxide. Examples beginning wth 16, Table XI, particularly 2G, 3G, etc., show the use of all three oxides so there are no blanks as in the first step of each stage where one oxide is missing. It is not believed any further explanation need be offered in regard to Table XI.

As previously pointed out certain initial runs using one oxide only, or in some instances two oxides, had to be duplicated when used as intermediates subsequently for further reaction. It would be confusing to refer in too much detail in these various tables for the reason that all pertinent data appear and the tables are essentially self-explanatory.

Reference to solvent and amount of alkali at any point takes into consideration the solvent from the previous step and the alkali left from this step. As previously pointed out, Tables XII, XIII and XIV give operating data in connection with the entire series, comparable to what has been said in regard to Examples 1E thorugh 6E.

The products resulting from these procedures may contain modest amounts, or have small amounts, of the solvents as indicated by the figures in the tables. If desired, the solvent may be removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene 33 oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifierent oxyalkylation, i.e., no attempt to selectively add one and then the other, or any other variant. v

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in whichbutylene oxide is used along with either one of the two oxides just mentioned, or a combination of both of them.

The same would be true in regard to a mixture of ethylene oxide and butylene oxide, or butylene oxide and propylene oxide.

The colors of the products usually vary from a reddish amber tint to a definitely red, amber and to a straw or light straw color. The reason is primarily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amber, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter colored products and the more oxide employed the lighter the color the product. Products can be prepared in which the final color is a lighter amber or straw color with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demulsification is concerned, or some other industrial uses, there is no justification for the cost of bleaching the product.

Generally speaking, the amount of alkaline catalyst present is comparatively small and it need not be removed. Since the products per se are alkaline due to the presence of a basic nitrogen, the removal of the alkaline catalyst is somewhat more difiicult than ordinarily is the case for the reason that if one adds hydrochloric acid, for example, to neutralize the alkalinity one may partially neutralize the basic nitrogen radical also. The preferred procedure is to ignore the present of the alkali unless it is objectionable or also add a stoichiometric amount of concentrated hydrochloric acid equal to the caustic soda present.

TABLE IX Composition before Composition at end E Oxides Oxides Molal ratio N o. 080, Oata- Sol- Oata- Sl- Theo.

Ex. 0S0, lyst, vent, 0S0, lyst, vent, EtO PrO BuO mol. No. lbs. EtO, PrO, BuO, lbs. lbs. lbs. EtO, PrO, BuO, lbs. lbs. to oxyto oxyto oxywt.

lbs. lbs. lbs. lbs. lbs. alkyl alkyl. alkyl suscept. susoept. suscept. compd compd. compd 15. 55 1. 0 15.60 15. 55 7. 75 1.0 15. 60 15. 55 7. 75 1.0 15.60 15.55 15. 50 1.0 15. 60 15. 55 15. 50 1.0 15. 60 15.55 23. 25 1. 0 15. 60 15.55 23. 25 1.0 15.60 15. .55 31.0 1.0 15. 60 15.55 31. 0 1.0 15.60 15. 55 46. 1.0 15.60 15.55 46. 5 1.0 15. 60 15.55 62.0 1.0 15. 60 16.10 1.0 16. 16.10 8. 05 1.0 16.10 16. 10 8.05 1. 0 16. 10 16. 10 16. 10 1. 0 16. 10 16. 10 16. 10 1.0 16. 10 16. 10 24. 1. 0 16. 1O 16. 10 24. 15 1. 0 16. 10 16. 10 32. 1.0 16. 10 16. 1O 32. 20 1. 0 16. 10 16. 10 40. 1.0 16. 10 16. 10 40. 25 1. O 16. 10 16. 10 64. 1. 0 16. 10 15.05 1.0 14. 95 15.05 15.05 1. 0 14.95 15.05 15.05 1. 0 14. 95 15. 05 30. 10 1. 0 14.95 15.05 30. 10 l. 0 14. 95 15. O5 45. 15 l. 0 14. 95 15. 05 45. 15 l. 0 14.95 15. 05 60.20 1. 0 14. 95 15. 05 60. 20 1. 0 14. 95 15. 05 75. 25 1. 0 14. 95 15. 05 75. 25 1.0 14.95 15.05 90. 30 1.0 14. 95 15.55 1. 5 15.60 15.55 15.5 1. 5 15. 60 15. 15.5 1. 5 15.60 15. 55 31.0 1. 5 15.60 15. 55 31. 0 1. 5 15. 15. 55 46. 5 1. 5 15. 60 15. 55 46. 5 1. 5 15. 60 15. 55 62.0 1. 5 15. 60 15. 55 62. 0 1. 5 15. 60 15. 55 77. 5 1. 5 15. 60 15. 55 77. 5 1. 5 15. 60 15.55 93.0 1. 5 15. 69 16. 10 1. 5 16. 16 16. 10 16.0 1. 5 16. 10 16. 10 16. 0 1. 5 16. 10 16. 10 32.0 1. 5 16. 10 16. 10 32. 0 1. 5 16. 10 16. 10 48. 0 l. 5 16. 10 16. 10 48.0 1. 5 16. 10 16. 1O 64. 0 1. 5 16. 1O 16. 10 64. 0 1. 5 16. 10 16. 10 80. 0 1. 5 16. 10 16. 10 80. 0 1. 5 16. 10 16. 10 96.0 1. 5 16. 10 15.05 1. 5 14. 15.05 15.0 1. 5 14.95 15.05 15. 0 1. 5 14.95 15.05 30.0 1. 5 14.95 15. 05 30. 0 1. 5 14. 95 15. 05 60. 0 1. 5 14. 95 15.05 60.0 1. 5 14. 95 15.05 75.0 1. 5 14. 95 15. 05 75. 0 1. 5 14.95 15.05 90.0 1. 5 14. 95 15.05 90. 0 l. 5 14. 95 15. 05 105. 0 1. 5 14. 95 0 15. 55 1. 5 15.60 15.05 5.0 1. 5 15.60 13. 9 4, 15. 55 5. 0 1. 5 15. 60 15.55 10.0 1. 5 15. 60 27. 8 5, 110 15.55 10. O 1. 5 15. 60 15. 55 15.0 1. 5 15.60 41. 7 6, 110 15. 55 15.0 1. 5 15.60 15.55 20.0 1. 5 15.60 55. 6 7, 110 15. 55 20. 0 1. 5 15. 60 15. 55 30. 0 1. 5 15. 60 83. 4 9, 110 15. 55 30. 0 1. 5 15. 60 15. 55 60. 0 1. 5 15. 60 166. 8 12, 110 16. 10 l. 5 16. 10 16. 10 8. 0 1. 5 16. 10 22. 2 4, 820 16. 1O 8. 0 1. 5 16. 1O 16. 1O 16. 0 1. 5 16. 10 44. 4 6, 426 16. 10 16. 0 1. 5 16. 1O 16. 10 24.6 1. 5 16. 10 66. 6 8, 020 16. 10 24. 0 1. 5 l6. 10 16. 10 32.0 1. 5 16. 10 88.8 9, 620 16.10 32.0 1. 5 16.10 16. 10 48.0 1. 5 16. 10 133. 2 12, 820 16. 10 48.0 1. 5 16. 10 16. 10 64. 0 1. 5 16. 10 177. 6 020 15.05 1. 5 14.95 15. 05 5.0 1. 5 14.95 13. 9 4, 010 15. 05 5. 0 1. 5 14. 95 15. 05 1O. 0 1. 5 14. 95 27.8 5, 010 15.65 10. 0 1. 5 14. 95 15.05 15. 0 1. 5 14. 95 41. 7 6, 010 15.05 15.0 1. 5 14. 95 15. 05 20. 0 1. 5 14. 95 55. 6 7, 010 15.05 20. 0 1. 5 14. 95 15. 05 40. 0 1. 5 14.95 111. 2 11, 010 15.05 40. 0 1. 5 14. 95 15. 05 60. 0 1.5 14.95 166. 8 15, 010

Theo. mol. wt.

BuO to oxyalkyl.

1623134604666666333333666666333333888888111111 moooo soooo Molal ratio PrO alkyl.

pt. suscept.

EtO

alkyl. suseept. susce compd. compd. compd.

to oxyto oxy- 333333 8 1 64 74 93 wooocccsooocw mnwmnlflmmwsms-bnwmmzfioe 11111111 2 12 12 .112 n Solvent, lbs.

Catalyst,

Composition at end Oxides lbs.

EtO, PrO, BuO, lbs.

lbs.

TABLE X 030, lbs.

Solvent, lbs.

Catalyst,

Oxides lbs.

0 50500 00000 WOOOOO 7 205" 80 6 4 2 8 Composition before EtO, IrO, BuO, lbs.

lbs.

080, lbs.

TABLE XI Composition before Composition at end o l Oxides M0121 ratio Ex. 050, c n 1. Oata- Sol- Theo. EL 050, lyst, vent, 0S0, lyst, vent, EtO PrO BuO mol. N0. lbs. EtO, PrO, BuO, lbs. lbs. lbs. EtO, PrO, BuQ, lbs. lbs. to oxyto oxyto oxywt.

lbS. lbs. lbs. lbs. lbs. lbs. alkyl. alk alkyl.

suscept. suscept. suscept. compd. compd. compd. 9-" 78F--- 15.55 60.0 30.0 1.5 15.60 15.55 5.25 60.0 30.0 1.5 15.60 23.9 206.56 83.4 22,160 2G.-- 78F--- 15.55 5.25 00.0 30.0 1.5 15.00 15.55 10.50 00.0 30.0 1.5 15.00 47.8 200.50 83.4 23,210 78F--. 15.55 10.5 60.0 30.0 1.5 15.60 15.55 15.75 60.0 30.0 1.5 15.60 71.7 206.56 83.4 24,260 4 78F.-- 15.55 15.75 60.0 30.0 1.5 15.60 15.55 21.00 60.0 30.0 1.5 15.60 95.6 206.56 83.4 25,310 6 78F--- 55 21.0 00.0 30.0 1.5 15.00 15.55 20.25 00.0 30.0 1.5 15.00 110.5 200.50 83.4 20,300 6G-.- 78F--- 15.55 20.25 00.0 30.0 1.5 15.00 15.55 31.50 00.0 30.0 1.5 15.00 143.4 200.50 83.4 27,410 83F--- 10.10 48.0 32.0 1.5 10.10 10.10 4.0 48.0 32.0 1.5 10.10 18.18 105.0 88.8 20,020 80... 8313... 10.10 4.0 48.0 32.0 1.5 10.10 16.10 8.0 48.0 32.0 1.5 10.10 30.30 105.0 88.8 20,820 9G--- F--- 10. 8.0 48.0 32.0 1.5 10.10 10.10 12.0 48.0 32.0 1.5 10.10 54.54 105.0 88.8 21,020 10 83F.-- 10.10 12.0 48.0 32.0 1.5 10.10 10.10 10.0 48.0 32.0 1.5 10.10 72.72 105.0 88.8 22,420 11G-- 83F..- 10.10 10.0 48.0 32.0 1.5 10.10 10.10 24.0 48.0 32.0 1.5 10.10 109.08 105.0 88.8- 24,020 12 83F.-- 10.10 24.0 48.0 32.0 1.5 10.10 10.10 48.0 48.0 32.0 1.5 10.10 218.10 105.0 88.8 ,820 871?... 15.05 20.0 40.0 1.5 14.05 15.05 5.0 20.0 40.0 1.5 14.05 22.73 09.0 111.2 10,010 14 87 15.05 5.0 20.0 40.0 1.5 14.05 15.05 10.0 20.0 40.0 1.5 14.05 45.40 00.0 111.2 17,010 1501.. 87F--. 15.05 10.0 20.0 40.0 1.5 14.05 15. 05 12.5 20.0 40.0 1.5 14.95 50.83 00.0 111.2 17,510 166.. 8713... 15.05 12.5 20.0 40.0 1.5 14. 05 15.05 15.0 20.0 40.0 1.5 14.05 08.2 00.0 111.2 18,010 176.- 87F 15.05 15.0 20.0 40.0 1.5 14.05 15.05 17.5 20.0 40.0 1.5 14.05 70.50 00.0 111.2 18,510 186.. 8713... 15.05 17.5 20.0 40.0 1.5 14. 05 15.05 20.0 20.0 40.0 1.5 14. 05 00.02 00.0 111.2 10,010 1%.. 58F--- 15.55 15.5 00.0 1.5 15.00 15.55 15.5 0.2 00.0 1.5 15.00 70.4 21.30 100.8 10,040 G-- 58F--- 15.55 15.5 0.2 00.0 1.5 15.00 15.55 15.5 12.4 00.0 1.5 15.50 70.4 42.72 100.8 17,880 210.. 5815... 15.55 15.5 12.4 00.0 1.5 15.00 15.55 15.5 15.5. 00.0 1.5 15.00 70.4 53.4 100.8 ,500 220:.. 58 15.55 15.5 15.5 00.0 1.5 15.00 15.55 15.5 24.8 00.0 1.5 15.00 70.4 85.44 100.8 10,740 236.- 58F--. 15.55 15.5 24.8 00.0 1.5 15.00 15.55 15.5 31.0 00.0 1.5 15.00 70.4 100.8 100.8 20,080 246.- 58 15.55 15.5 31.0 00.0 1.5 15.00 15.55 15.5 40.5 00.0 1.5 15.00 70.4 100.2 100.8 24,080 256.- 05 10.10 24.0 43.0 1.5 10.10 10.10 24.0 8.05 48.0 1.5 10.10 109.2 27.8 133.2 19,230 20 65F... 10.10 24.0 8.05 48.0 1.5 10.10 10.10 24.0 10.10 48.0 1.5 10.10 100.2 55.0 133.2 20,840 276.. 10.10 24.0 10.10 48.0 1.5 10.10 15.10 24.0 24.15 48.0 1.5 10.10 100.2 83.4 133.2 22, 450 23 66F-.. 10.10 240 24.15 48.0 1.5 10.10 10.10 24.0 32.20 48.0 1.5 10.10 100.2 111.2 133.2 24,000 29 F.-- 10.10 24.0 32.20 48.0 1.5 10.10 10.10 24.0 40.25 48.0 1.0 10.10 100.2 130.2 133.2 25,070 30 051... 10.10 24.0 40.25 48.0 1.5 10.10 10.10 24.0 48.30 48.0 1.5 10.10 109.2 166.8 133.2 27,280 31 7113... 15.05 30.0 00.0 1.5 14.05 15.05 30.0 3.0 00.0 1.5 14.95 103.5 10.35 166.8 22,810 326.. 71F... 15.05 30.0 3.0 00.0 1.5 14.05.15.05 35.0 0.0 00.0 1.5 14.95 103.5 20.70 100.8 .410 330.. 71 15.05 30.0 0.0 00.0 1.5 14.95 15.05 30.0 0.0 00.0 1.5 14.05 103.5 31.05 100.8 24,010 340.. 71 15.05 30.0 9.0 00.0 1.5 14.05 15.05 30.0 12.0 00.0 1.5 14.05 103.5 41.4 100.8 24, 010 350.- 71 15.05 30.0 12.0 00.0 1.5 14.05 15.05 30.0 18.0 00.0 1.5 14.05 103.5 02.10 100.8 25,810 366.- 71 15.05 30.0 18.0 00.0 1.5 14.05 15.05 30.0 30.0 00.0 1.5 14.05 103.5 124.2 166.8 20,410

TABLE XII Max. Max. Solubility Ex. temp., pres., Time, No. 0. p. 8.1. hrs.

7 Water Xylene Kerosene 1E -130 10-15 M Insoluble Insoluble.

125-130 10-15 V Emulsiflable D0. 125-130 10-15 do Do. 411. 125-130 10-15 D0. 5E 125-130 10-15 D0. 6E 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 D0. 125- 10-15 Do. 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 Do. 125-130 10-15 Soluble.

125-130 10-15 Do 125-130 10-15 Insoluble 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 Soluble. 125-130 10-15 Do. 125-130 10-15 Insoluble. 125-130 10-15 Do. 125-130 10-15 D0. 125-130 10-15 D0. 125-130 10-15 Soluble. 125-130 10-15 D0 -150 10-15 Insoluble 140-150 10-15 Do. 140-150 10-15 Do. 140-150 10-15 D0. 140-150 10-15 Do. 140-150 10-15 Soluble 140-150 10-15 Insoluble. 140-150 10-15 D0. 140-150 10-15 D0. 140-150 10-15 D0. 140-150 10-15 D0. 140-150 10-15 Soluble 49E 140-150 10-15 Insoluble. 50E 1 10-150 10-15 D0. 51E 140-150 10-15 Do. 52E 1 10-150 10-15 Do. 140-150 10-15 D0. 140-150 10-15 Soluble. 

1. A 3-STEP MANUFACTURING METHOD INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A POLYEPOXIDE CONTAINING AT LEAST TWO 1,2-EPOXY RINGS; AND (3) OXYALKYLATION WITH AN ALPA-BETA MONOEPOXIDE; SAID FIRST MANUFACTURING PROCESS BEING A STEP OF (A) CONDENSING (A) A FUSIBLE, NON-OXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCEW OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 